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A novel method was developed for the preparation of arborescent (dendritic graft) polymers, by successive grafting reactions of linear chain segments using alkyne-azide “click” chemistry coupling. A linear polystyrene substrate was thus randomly functionalized with acetylene functionalities, by acetylation and further reaction with propargyl bromide in the presence of potassium hydroxide and 18-crown-6 in toluene. The anionic polymerization of styrene was achieved with 6-tert-butyldimethylsiloxy-hexyllithium to obtain polystyrene with a protected hydroxyl chain end. Deprotection of the hydroxyl group, followed by conversion into tosyl and azide functionalities yielded the material serving as side chains in the grafting reactions. Coupling of the azide-terminated side chains with the acetylene-functionalized substrate in the presence of a Cu(I) catalyst proceeded in up to 93% yield. Additional cycles of substrate functionalization and side chain coupling led to arborescent polymers of generations G1 and G2, with low polydispersity indices (Mw/Mn≈ 1.1), in 60-84% yield. These polymers are characterized by a very compact structure, and molecular weights increasing geometrically over successive generations. A similar methodology was also shown to work for the synthesis of arborescent polybutadiene systems, using azide-functionalized substrates and alkyne-terminated side chains. The coupling reaction proceeded in up to 76% yield under optimized conditions for these systems.
ZnO nanoparticles were prepared by a green electrochemical synthesis method applying low current densities followed by a thermal treatment. Sodium polystyrene sulphonate (PSS) was used as stabilizer in the electrolytic aqueous medium due to its biocompatibility and stability. The as-prepared nanocolloids were then annealed to improve their stability, and then converted via hydroxide species into stoichiometric oxide. Different calcination temperatures were studied. ZnO@PSS nanomaterials were deposited onto SiO2/Si substrates, in part in combination with an organic semiconductor layer to evaluate their influence on organic field effect transistors (OFETs). All nanomaterials and composite layers were characterized by morphological and spectroscopic techniques. Promising results regarding the use of ZnO@PSS in OFETs could be demonstrated.
A photoactivated ZnO nanomesh with precisely controlled dimensions and geometries is fabricated by using nanosphere lithography process. The nanomesh structures effectively increase the surface-to-volume ratio to improve the sensing response under the same testing gas. And the periodical nanostructures also increase the effective light path and lead to more efficient light activation for gas sensing. With the increase of the photoinduced oxygen ions by UV illumination, a distinguished sensing response is observed at room temperature. In the optimized case, the sensing response (△R/R0) of the ZnO nanomesh at the butanol concentration of 500 ppm is 97.5%, which is 4.54 times higher than the unpatterned one.
Uranium-plutonium mixed oxides incorporating high amounts of plutonium are considered for future nuclear reactors. For plutonium content higher than 20%, a phase separation occurs, depending on the temperature and on the oxygen stoichiometry. This phase separation phenomenon is still not precisely described, especially at high plutonium content. Here, using an original in situ fast X-ray diffraction device dedicated to radioactive materials, we evidenced a phase separation occurring during rapid cooling from 1773 K to room temperature at the rate of 0.05 and 2 K per second for a (U0.55Pu0.45)O2-x compound under a reducing atmosphere. The results show that the cooling rate does not impact the lattice parameters of the obtained phases at room temperature but their fraction. In addition to their obvious fundamental interest, these results are of utmost importance in the prospect of using uranium-plutonium mixed oxides with high plutonium content as nuclear fuels.
An epitaxial shell of cadmium sulphide is grown on lead sulphide quantum dots in order to reduce the concentration of surface defects. Thin solid films of these core/shell materials are found to have low carrier concentrations due to effective surface passivation which reduces the number of dangling bonds. In this paper PbS/CdS is used as a quasi-intrinsic layer in p-i-n photovoltaic devices where PbS acts as the p-layer and ZnO the n-layer. By studying different permutations of these layers and the degree of PbS p-type doping by annealing we optimise fill factor and open-circuit voltage.
The covalent functionalization of photosynthetic proteins with properly tailored organic molecular antennas represents a powerful approach to build a new generation of hybrid systems capable of exploiting solar energy. In this paper the strategy for the synthesis of the tailored aryleneethynylene organic fluorophore (AE) properly designed to act as light harvesting antenna is presented along with its successful bioconjugation to the photosynthetic reaction center RC from the bacterium Rhodobacter sphaeroides .
Carbon supported Pt-SnO2 electrocatalysts with different Sn/Pt molar ratios were prepared by an electron beam irradiation method. Dissolved gas conditions in the vials irradiated with electron beam were controlled to air or Ar. The results of the material analyses showed that both Pt and SnO2 were immobilized onto carbon support in all catalysts. Bubbling Ar to the precursor solution led to steady change of metal contents in response to the precursor concentrations. The ethanol oxidation activity plotted against Sn/Pt ratio behaved differently with dissolved gas condition of the vial. This difference is discussed with supposed existing state of SnO2 in connection with the reduction process of Pt and Sn.
Topographical features are known to influence the axonal outgrowth of neurons. Understanding what kinds of topographical features are most effective at growth cone guidance and how outgrowth responds to these structures is of great importance to the study of nerve regeneration. To this end we analyze axonal outgrowth on tilted nanorod substrates which have been shown to impart directional bias to neuron growth. We utilize the Atomic Force Microscope to characterize the surface features present on these substrates and how such features are influencing the axonal outgrowth. Additionally, using a model which considers the neuronal growth cone as an object influenced by an effective potential we determine an effective force imparted on the growth cone by the surface topography.
Carbon nanotubes (CNT) are expected to revolutionize a range of technologies because of their unique mechanical and electrical properties. Using nanotubes in structural materials holds significant promise due to their extremely high modulus and tensile strength, however their cost, production rate and integration into a fiber form severely limit the current structural application opportunities. The high cost of CNT is tied to their slow, batch synthesis using vapor phase, vacuum processes. We report the investigation of the formation of carbon nanotubes from a polymeric precursor using an electrospinning production process. Electrospinning generates nanofibers at velocities up to 10 m/s from a single nozzle without a vacuum requirement, with the potential to generate CNT appropriate from structural and electrical applications. Our CNT formation concept is based upon Reactive Empirical Bond order calculations that show carbon nanofibers have a thermodynamic preference for the cylindrical graphite conformation. Simulations suggest that for small diameter carbon fibers, less than about 60 nm, the single wall and multi wall nanotubes (SWNT and MWNT) phases are thermodynamically favored relative to an amorphous or planar graphitic nanofiber structure. We have developed a novel process using continuous electrospun polyacrylonitrile (PAN) nanofibers as precursors to continuous SWNT and MWNT. The process for converting PAN nanofibers to SWNT's and MWNT's follows the process for typical carbon fiber manufacture. The PAN nanofibers, of 10 to 100 nm in diameter, are crosslinked by heating in air and then decomposed to carbon via simple pyrolysis in inert atmosphere. The pyrolyzed carbon nanofibers are then annealed to form the more energetically favorable SWNT or MWNT phase, depending upon the precursor diameter. We will discuss the process and characterization data.
Spectroscopy technique is used for various applications, for example in archaeology, in order to analyze samples of floors, including material excavation sites. In this work the floor samples that were found in two rooms belonging to a house in a residential Hispanic area, at different stratigraphic levels corresponding to the classical period, as well as samples that were collected in two deposits of lime (El Refugio and El Llano) around the site mentioned were analyzed. The characterization of the samples of the archaeological site Chingú in Tula de Allende in the state of Hidalgo was carried out by using Scanning Electron Microscopy (SEM) to observe the morphology of the samples and Energy Dispersive X-ray Spectroscopy (EDS) to analyze the composition of cementitious material of the floors and natural material of lime deposits. Comparing these samples with other archaeological works of literature, the morphology and composition of manufactured floors will be discussed.
Coahuilite, a new variety of amber is described from the Late Cretaceous Olmos Formation (ca. 73 Ma.), Coahuila, north of México. This amber is totally distinct chemically and stratigraphically from the Miocene Chiapas amber (ca. 23-13 Ma.), Southern México, which according to mineral nomenclature is currently known as Simojovelite var. nov. Additionally, an emended description of Bacalite is proposed, based on the physicochemical analysis and geological record of a fossil resin recently recovery from the Late Cretaceous El Gallo Formation (ca. 73 Ma.), Baja California, northwestern México. The results are supported by characterization of such ambers using synchrotron-based Infrared (FTIR) microspectroscopy.
We present an integrated readout technique for interrogating the suspension height of micro-electro-mechanical systems (MEMS) structures. This readout technique is envisaged to be useful in applications such as MEMS-based biological and chemical sensing, where it is necessary to obtain the accurate position of a MEMS beam. The approach is based on the suspended MEMS structure modulating light transmission in an underlying optical waveguide via Fabry-Perrot phenomena. The performance of the technique is predicted via finite difference time domain (FDTD) simulations the results of which are confirmed by experimental measurements.
Cartilage is a complex biological tissue that exhibits gel-like behavior. Its primary biological function is providing compressive resistance to external loading and nearly frictionless lubrication of joints. In this study, we model cartilage extracellular matrix using a biomimetic system. We demonstrate that poly(vinyl) alcohol (PVA) hydrogels are robust biomaterials exhibiting mechanical and swelling properties similar to that of cartilage extracellular matrix. A comparison is made between the macroscopic behavior of PVA gels and literature data reported for cartilage.
The aim of the present study is to analyze interfacial adhesion and characterize the tensile properties of a FML elaborated from thin layers of an aluminum alloy and layers of maleic anhydride modified polypropylene (MAHPP) reinforced with an aramid woven fabric. For the analysis of interfacial adhesion, a microbond test is carried out on the MAHPP-aramid fiber system and a single lap joint test is performed on FML constituent materials, as well as the tensile characterization of the FML and its constituents is conducted accordingly. Microbond testing revealed an improvement in interfacial shear strength for the MAHPP-aramid fiber system in comparison with that of polypropylene-aramid fiber systems reported in the literature. The apparent shear strength between the FML constituent materials is comparable to that for bonding of aluminum with MAHPP. Tensile characterization of the FML and its constituents showed that the FML presented greater tensile strength than the aluminum alloy; and a more ductile behavior in comparison with its individual components due to the degree of adhesion between the constituents which allows the material to deform in unison.
Combining high resolution transmission electron spectroscopy, electron diffraction, and resonant Raman spectroscopy experiments on the same suspended (free-standing) individual carbon nanotubes is the ultimate approach to relate unambiguously the structure and the intrinsic phonon features of these nano-systems.
By using this approach, the effect of coupling between nanotubes on the phonons is investigated in two model nano-systems: (i) a bundle of two non-identical SWNTs (inhomogeneous dimer), (ii) double-walled carbon nanotubes.
Hydrogel actuators were prepared by combining ionoprinting technique with reversible metal ion coordination chemistry found in mussel adhesive proteins. Hydrogels were formulated with biomimetic dopamine moiety, which contains a catechol side chain that is capable of forming mono-, bis-, and tris-complexes with ferric (Fe3+) ions with increasing pH. Catechol-Fe3+ complexation increased local crosslinking density, which induced hydrogel bending at the site of Fe3+ ionoprinting. The effect of pH on the dynamic response of hydrogel actuation was tracked by following the radius of curvature at the ionoprinting site. Both the rate of change and the maximum radius of curvature increased when the pH with increasing pH (2.5-9.5), indicating that pH can be used to modulate hydrogel actuation. Additionally, hydrogels containing Fe3+ demonstrated higher extent of deswelling when equilibrated at a basic pH. Similarly, dynamic mechanical analysis in the compression mode revealed that both the storage and loss modulus values for Fe3+-containing hydrogels increased with increasing pH. These results indicated that bis- and tris-complexes formed at an elevated pH level contributed to a faster rate of actuation and a more condensed network architecture. Hydrogel actuation and deswelling were also observed at pH of 3.5 although to a lesser degree, potentially due to a stronger affinity between network-bound catechol and Fe3+ ions as compared to complexes formed in a dilute solution.
Drug delivery systems are becoming increasingly sophisticated, with the ability to target and penetrate specific tissues and release drugs based upon the local environment. While these advanced systems often offer advantages over their less sophisticated counterparts, the final product may be more complex and require additional manufacturing steps. In this article, we review a body of work based on genetically encoded elastin-like polypeptides (ELPs) that offer a route to modular, multifunctional delivery systems that are simple to manufacture. ELPs are temperature-sensitive biopolymers that can be designed on the genetic level and expressed in cell-based protein production systems. The tools of molecular biology and versatility of proteins are used to engineer polymers with precise composition and molecular weight that self-assemble to form drug delivery systems with an impressive variety of features and functions. Due to their versatility and ease of production, ELPs are likely to contribute to the goal of designing simple and effective “smart” delivery systems.